Azo derivatives of carbostyril



Patented June 2, 1953 AZ O DERIVATIVES OF CARBOSTYRIL Joseph SerutQMeriden, Conn., assignor to American Cyanamid Company, New York, N. Y., a

corporation of Maine No Drawing. Application June 17, 1949,

1 Serial No. 99,863

13 Claims. (Cl. 260155) This invention relates to new azo coloring matters containing the carbostyril nucleus.

In the past it has been considered impossible to produce azo coloring matters containing the carbostyril nucleus because carbostyril-is in-ca pable of coupling with diazo compounds except when the nucleus contains other activating groups.

The compounds of the present invention may be represented by the following structural formula:

in which R is the radical of a functionally saturated hydrocarbon and Ar is an aromatic radical having a metallizable group ortho to the azo group. The carbon atoms of the benzo ring may be substituted by groups such as alkyl, aryl, halogen, nitro, amino or carboxyl.

The preferred compounds of the present invention are those in which the aromatic radical is sulfonated as they can be used in the dyeing of basic nitrogenous fibers; and preferably contains a metallizable group ortho to the azo linkage, thus permitting metallization.

While it is not intended to limit the new colouring matters of the present invention to a particular method of preparing the new series, it has been made possible by the use'of a new process which in a more specific aspect of the present invention is claimed. This process, which is particularly useful in preparing preferred sulfonated dyestuffs, involves coupling an acylacetic arylide with a diazo component and the closing of the heterocyclic portion of the carbostyril nucleus by cyclization in the presence of a condensing agent, preferably concentrated sulfuric acid.

It is an important advantage of the present invention that the cyclization reaction proceeds very easily and is widely applicable to azo compounds from acylacetic arylides with a few obvious restrictions which will be set out below.

In general the azo compounds can be dissolved in concentrated sulfuric acid and cyclization is rapidly effected by heating for a short time at a moderate temperature, for example 60 to 100 C. The reaction is so fast that in some cases it may be complete in as little as ten minutes and onlyrarely are reaction times materially exceeding an hour necessary.- In some cases the product crystallizes out of solution and can be filtered from the concentrated sulfuric acid. In other cases it is necessary to drown the reaction mixture in ice Water and recover the product by filtration, salting out if necessary.

In order to produce. the preferred sulfonated compounds of the present invention it is often convenient to start with an azo compound containing at least one sulfonic group. However, this is not always necessary as in some cases sulfonation is effected during cyclization and in other cases may readily be effected after .ring closure is complete.

In general the diazo component used in making the azo compound which is ring closed to form the coloring matters of the present invention may be derived from any diazotizable arylamine such'as aniline and its homologs, sulfanilic acid, metanilic acid, anthranilic acid, 4-sulfonanthranilic acid, 5-sulfoanthranilic acid, o-aminophenol, oand p-anisidine, 2-aminophenol-4-sulf-om'c acid, 2 -amino-4-ch1o-rophenol, 2-amino-4-chlorophenol-5-sulfonic acid, 2-amino-4-chlorophenol-6- sulfonic acid, 2-amino-4-nitrophenol, 2-amino- 4-nitrophenol-5-sulfonic acid, 2-amino-4-nitrophenol-fi-sulfonic acid, 2-amino-5-nitrophenol, 2-amino-4-methyl-6-nitrorihenol, 2-amino-6-nitrophenol-4-sulfonic acid, lamino-Z-naphthol- 4-su1fonic acid, naphthionic acid, l-naphthylamine-G-sulfonic acid, l-amino-fi-nitro-Z-naphtholl-sulfonic acid, o-dianisidine, 4-chloro-2- aminoanisole, and 4-nitro-2-choroaniline.

The only restriction on the acylaceti-c arylide used as a coupling component to produce the azo compound is to have a free ortho position to permit ring closure. It is an advantage of the present invention thatexcept for the limitation above any acylacetic arylide may be used. Typical of such'compounds are the acetoa-cetyl and benzoylacid, acetoacetanilide-2,5-disulfonic acid, aceto acetyl anthranilic acid, propionylacetanilide, benzoylacetic p-phenylanilide, p-methylbenzoylacetic anilide, p-methoxybenzylacetanilide, pphenylbenzoylacetanilide, anilide, and (acetoacetylamino) may also be-used.

It is an additional featurezo'f. the presentins beta-naphthoylakzetnaphthalene,-

vention that the azo carbostyril compounds prepared as described, are useful not only as dyestufis and pigments in themselves, but can readily be metallized if the diazo component is substituted ortho to the azo linkage by a metallizable group, such as hydroxyl, methoxyl, halogen, or carboxyl- Rhe resulting metal complexes show good all-round fastness; the preferred sulfonated compounds show also good dyeing properties in a variety of shades. The chromium complexes are particularly valuable and. may be. prepared; by known methods. Other metal complexes, such as nickel and copper complexes, mayialso be prepared from the corresponding salts.

The present invention is illustrated in detail in the following examples. Parts are by weight.

Example 1 C H: O H

N.=N SQsH O H 3H3 l qoz A solution of 45.2 partsof 2-amino-4-nitrophenol-fi-su-lionic acict in 480 parts of water. and 127 parts of 1.0% sodium carbonate solution is treated with 38. parts. t concentrated hydro:- chl'oric acid, cooled to 5:-l0 C., and. diazotized in the. normal manner withSN- sodium nitrite. Any excess: of. nitrite. is destroyed with sulfamic acid. The diazo is then added rapidly at 540 to a solution. of 40. parts of acetoacet o-toluidide. in 600 parts oi water and 33 parts of 5N sodium hydroxidesolution. Coupling rapid and complete. The; reaction mixture is heated to 50 (3., acidified topH- 5-7 with 5N sulfuric acid, stirred tenminutes, filtered: hot, washed and dried at 60. The resulting product dyes wool yellow.

Forty parts. ofv the, dyestufi thus prepared are stirred into 110 parts of concentrated sulfuric acid. The. mixture is then slowly and carefully heated Afterfiile minutes at 75 C.,, crystallization takes place. The mixture is cooled to. 50 and filtered. The resulting dark red azo carbostyril dyestufii may be metallized by refluxing in chromic acetate solution according to the procedure given in Example; 3'.

Example 2 SOaH Z amino-Gmitrophenol--sulionic acid is, di azot-izedand coupled with acetoacet-o-tolu-idide according to the procedure described in Example 1. Seventy parts of theresulting yellow. crystalline dyestuff. is stirred into 137 partsofconcentrated sulfuric acid. The mixture is then stirred at 60 C.. forv one hour, cooled. to 40 (3., and. drowned in 4.00 parts of ice water. The product is filtered, Washed with water, and purifi'ed by slurrying' in .acetone and filtration. It is a reddish homogeneous; crystalline material which dyes wool reddish-orange; It can be metalli'zed by refluxing in chromium acetate so lution, according to the procedurewhich is dc.- scribed in detail in Example; 3;.

Example 3 SOaH 1-amino-2-naphthol-3,6-disulfonic acid is diazotized and coupled with acetoacet-p-toluidide according tothe procedure described in Example 1. Fifteen parts of the resulting orange dyestufiis added in portions to 49 parts of concentrated sulfuric acid. The resulting mixture is carefully heated to -85 0., kept at this temperature about five minutes, and then drowned inv Water. The product is filtered, washed with 10% sodium chloride solution, and dried. It gives bluish red dyeings on nylon and wool. As a chrome dye it gives garnet to Bordeaux shades.

Metallization of this, and other dyestufis of the present inizentiomis carried out with the aid of a chromium acetate solution which is prepared in the following way: Chromic acid (186 parts) is dissolved-m 1156; parts of water. To the solution isadded 163 parts of glacial acetic acid and 50 parts of glucose. The solution is. then slowly heated to the boil and gently boiled until the chrom-ic. acid 'iscompletely reduced. After cooling, the solution. is diluted. to the volume of 2000 parts of water.

The above prepared azo carbostyril compound (30.3 parts) is metallized by refluxing eighteen hours in 300 parts of water containing 60 parts of 20% sodium acetate solution, parts of the above prepared chromium acetate solution, and parts of 90% formic acid. The solution is then diluted, cooled, and filtered. The metallized dyestufi. dyes wool Bordeauxshades.

Example 4 The dyestufi of the-abovefstructure;isprepared from. 1.-amino -2-naphthol3,5.-disulfonic acidand acetoacet-oetoluidide by the process of Example 3. The chromium complex. gives wool dyeings of Bordeauxshades...

Example 5.

chrome dyeings. It can be metallized according to the general procedure described in Example 3.

Ezcample 6 2 aminophenol 4 sulionic acid is diazotized and coupled with acetoacet-p-toluidide according to the general procedure described in Example 1. Thirty parts of the resulting dyestuii is added at room temperature to 73 parts of concentrated sulfuric acid. When the spontaneous temperature rise has subsided, the mixture is cautiously heated to 80-85, maintained at this temperature for ten minutes, allowed to cool, and filtered. The orange-red product is washed with acetone. It gives brown chrome dyeings. It may be metallized by the general procedure described in Example 3.

Example 7 on \N SO3H v2-aminophenol-4-sulfonic acid is diazotized and coupled with acetoacetanilide. The product is cyclized according to the procedure of Example 6, and the resulting azo car-bostyril dyestuff, of the above formula, metallized according to the general procedure of Example 3.

Example 8 1-amino-2-naphthol4-sulfonic acid is diazotized and coupled with acetoacet-p-toluidide. The product is cyclized according to the procedure of Example 2. It gives brown to olive chrome dyeings, and may be metallized according to the general procedure of Example 3.

Iclaim:

l. A 3-arylazo carbostyril substituted in the 4 position by the radical of a functionally saturated hydrocarbon.

2. An arylazo carbostyril according to claim 1 having a metallizable grou ortho to the azo group selected from the group consisting of a hydroxyl, methoxyl, halogen and carboxyl.

3. A compound according to claim 2 in which the aryl radical is sulfonated.

4. A compound according to claim 3 having the formula in which R is a functionally saturated hydrocarbon radical and Ar is an aromatic radical having a metallizable group ortho to the azo group.

5. A compound having the following formula R,- N=NR \N OH 9. A dyestuff of the formula 10. A process of cyclizing an acylacetic arylide, containing a free position ortho to the amide nitrogen, and substituted in the alpha position by an arylazo radical containing at most two carbocyclic rings, to the corresponding 3-arylazocarbostyril, by heating in concentrated suliuric acid until ring closure is efiected.

11. A process according to claim 10 in which the arylide is an anilide.

12. A process according to claim 10 in which the arylazo group is sulfonated and is substituted ortho to the azo linkage by a metallizable substituent selected from the group consisting of hydroxyl, methoxyl, halogen, and carboxyl.

13. A process according to claim 10 in which the arylide is an acetoacetanilide.

JOSEPH SERUTO.

References Cited in the file of this patent UNITED STATES PATENTS- Number Name Date 1,052,031 Blank Feb. 4, 1913 1,775,644 Krammerer et a1. Sept. 16, 1930 1,908,571 Straub et a1. May 9, 1933 2,364,347 Dickey et a1. Dec. 5, 1944 FOREIGN PATENTS Number Country Date 20,530 Great Britain of 1895 28,716 Great Britain of 1909 OTHER REFERENCES Hollins Synthesis of Nitrogen Ring Compounds, 1924, pages 266, 267 and 269. 

8. A DYESTUFF OF THE FORMULA 